Spatially Resolved Spontaneous Reactivity of Diazonium Salt on Edge and Basal Plane of Graphene without Surfactant and Its Doping Effect

The site-dependent and spontaneous functionalization of 4-bromobenzene diazonium tetralluoroborate (4-BBDT) and its doping effect on a mechanically exfoliated graphene (MEG) were investigated. The spatially resolved Raman spectra obtained from both edge and basal region of MEG revealed that 4-BBDT molecules were noncovalently functionalized on the basal region of MEG, while they were covalently bonded to the edge of MEG. The chemical doping effect induced by noncovalently functionalized 4-BBDT molecules on a basal plane region of MEG was successfully explicated by Raman spectroscopy. The position of Fermi level of MEG and the type of doping charge carrier induced by the noncovalently adsorbed 4-BBDT molecules were determined from systematic G band and 2D band changes. The successful spectroscopic elucidation of the different bonding characters of 4-BBDT depending on the site of graphene is beneficial for the fundamental studies about the charge transfer phenomena of graphene as well as for the potential applications, such as electronic devices, hybridized composite structures, etc.